KR101616968B1 - Functionalized nanoparticles and method - Google Patents

Abstract

Nanoparticles comprising an inorganic core comprising at least one metal and / or at least one semiconductor compound comprising at least one metal include a coating or shell disposed over at least a portion of the core surface. The coating may comprise one or more layers. Each coating layer may comprise a metal and / or one or more semiconductor compounds. The nanoparticles further comprise a ligand attached to the surface of the coating. The ligand is represented by the formula X-Sp-Z wherein X is a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group, a phosphone or an arsonic group, Z represents a group capable of transferring (i) a specific chemical property to a nanoparticle, such as, for example, an acid group, a phosphate group or an arsenate group, a phosphine or arsine oxide group, And / or (ii) a reactive group that provides specific chemical reactivity to the surface of the nanoparticles and / or (ii) a cyclic, halogenated and / or polar amphoteric group. In certain embodiments, at least two chemically distinct ligands are attached to the surface of the coating, wherein at least two ligands (I and II) are represented by the formula X-Sp-Z. In the ligand (I), X represents a phosphone, phosphine or phosphate group, and in the ligand (II), X represents a primary or secondary amine or imidazole or amide. In both ligands (I) and (II), Sp, which may be the same or different in the two compounds, represents a spacer group, such as a group or a group capable of transferring charges, and Z, which may be the same or different in the two compounds, Is a group selected from groups capable of delivering specific chemical properties to the nanoparticle as well as providing specific chemical reactivity to the surface of the nanoparticle. In a preferred embodiment, the nanoparticles comprise a core comprising a semiconductor material.

Description

[0001] FUNCTIONALIZED NANOPARTICLES AND METHOD [0002]

Priority claim

This application is related to U.S. Serial No. 60 / 971,887, filed September 12, 2007; 60 / 992,598 (filed December 5, 2007); And 61 / 083,998 filed on July 28, 2008, each of which is incorporated herein by reference in its entirety.

This application is also a continuation-in-part application of co-owned International Application No. PCT / US2007 / 013152 (filed June 4, 2007) (published in English on PCT Publication No. WO 2007/143197 on December 13, 2007) . PCT applications are described in co-owned U.S. Patent Application No. 60 / 810,767 filed June 2, 2006, 60 / 810,914 filed June 5, 2006, 60 / 804,921 filed June 15, 60 / 825,373 (filed on September 12, 2006), 60 / 825,374 (filed on September 12, 2006), 60 / 825,370 (filed on September 12, 2006) and 60 / 886,261 (filed January 23, 2007) Claiming priority.

Technical field

The present invention relates to the technical field of nanoparticles, more particularly nanoparticles comprising ligands and related methods.

The main synthesis method of colloidal quantum dots is the use of high boiling solvents such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), aliphatic phosphone or carboxylic acid, and aliphatic amine species Lt; / RTI > Thus, the ligand capping group on the surface of the quantum dots is thought to be a statistical distribution of TOPO, TOP, acid and amine. Throughout the quantum dot literature, in order to influence the surface chemistry change (e.g., making a water soluble quantum dot) on a particular quantum dot sample, a typical procedure involves a cap exchange reaction, The proton point (core or core-shell) is present in the solution of the other ligand and is heated for a long period to replace the existing ligand and replace it with a replacement species, which is replaced with a replacement. This procedure can be detrimental to maintaining the optical properties of the quantum dots and often significantly reduces emission efficiency and stability.

An alternative technique is to use self-assembled colloidal particles that surround and interlock with natural quantum dot surface ligands. A disadvantage of this method is that a polar solvent environment is required to produce encapsulated colloidal particles and thus the technology is limited to aqueous based applications such as biological tagging and imaging.

Thus, there is a continuing need for semiconductor nanocrystals including functionalized ligands compatible with organic based solvent systems and methods for their preparation.

SUMMARY OF THE INVENTION

The present invention relates to nanoparticles comprising one or more ligands attached to the surface of the nanoparticles. The present invention also relates to a process for preparing nanoparticles in the presence of one or more ligands.

According to one aspect of the invention there is provided a nanoparticle comprising at least one chemically distinct natural ligand attached to its surface, wherein at least one of said ligands is represented by the formula:

X-Sp-Z

Wherein X is a group selected from the group consisting of a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group, a phosphone or arsonic group, a phosphine or arsinic acid group, , A phosphine or arsine oxide group, Sp represents a spacer group such as a group capable of transferring charge or an isolator, and Z represents (i) not only capable of transferring a specific chemical property to a nanoparticle, A reactive group that provides chemical reactivity and / or (ii) a cyclic, halogenated and / or polar amphoteric group wherein Z is not reactive when exposed to light in all cases.

"Natural ligand" as used herein refers to a ligand that attaches or coordinates to the nanoparticle surface during growth or overcoating thereof. Ligands are considered to be chemically distinct when they have different chemical compositions.

In certain embodiments, Z does not render the nanoparticles dispersible in a liquid medium comprising water.

In certain embodiments, the reactive group is a functional, bifunctional or multifunctional reagent. And / or reactive chemical groups.

As used herein, a "reactive chemical group" refers to a chemical group capable of reacting with one or more other groups or species. Examples of reactive chemical groups include functional substituents. Examples of the functional substituent include, but are not limited to, thiol, carboxyl, hydroxyl, amino, amine, sulfo, bifunctional group, polyfunctional group and the like.

In certain embodiments, the cyclic group may include a saturated or unsaturated cyclic compound (including, but not limited to, a single ring, bi-cyclic structure, multi-cyclic structure, etc.) or an aromatic compound. In certain embodiments, the cyclic group may comprise one or more heteroatoms. In certain embodiments, cyclic groups may include one or more substituents (including, but not limited to, reactive chemical groups, organic groups (such as alkyl, aryl, etc.), and the like. Other examples of cyclic groups are provided herein.

In certain embodiments, the halogenating group may include a fluorinating group, a perfluorinating group, a chlorinating group, a perchlorating group, a brominating group, a perbrominating group, an iodinating group, a periodating group and the like. Other examples of halogenating groups are provided herein.

In certain embodiments, the polar aprotic group may comprise a ketone, aldehyde, amide, urea, urethane or imine. Other examples of polar aprotic magnetic groups are provided herein.

In certain embodiments, the nanoparticles may comprise a semiconductor material.

In certain embodiments, the nanoparticles may include a core comprising a first material and a shell (or coating material) disposed over at least a portion of the core surface and comprising a second material. In certain embodiments, the first material comprises a semiconductor material. In certain embodiments, the second material comprises a semiconductor material. In certain embodiments, one or more additional shells are disposed over at least a portion of the shell surface.

In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals (semiconductor nanocrystals are also referred to as quantum dots). In certain embodiments, the semiconductor nanocrystals may include a core comprising a first material and a shell (or coating material) disposed over at least a portion of the core surface and comprising a second material. Preferably, the second material comprises a nanocrystalline semiconductor material. In certain embodiments, one or more additional shells are disposed over at least a portion of the shell surface. Further references to nanoparticles and semiconductor nanocrystals are provided herein.

Preferred ligands include benzylphosphonic acid, a benzylphosphonic acid containing one or more substituents on the ring of the benzyl group, a pair of such acids, and mixtures comprising at least one of the foregoing. In certain embodiments, the ligand comprises a 4-hydroxybenzylphosphonic acid, a conjugate of such an acid, or a mixture thereof. In certain embodiments, the ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate of such an acid, or a mixture thereof.

Another preferred ligand comprises a ligand represented by the formula X-Sp-Z, including an organic amine or a fluorinated organic amine comprising a terminal hydroxyl group.

In certain preferred embodiments, the nanoparticles comprise a semiconductor nanocrystal core comprising a first semiconductor material and an overcoat material comprising a second semiconductor material disposed over at least a portion of the core surface, Lt; / RTI > in the presence of one or more ligands as described above.

In certain embodiments, the nanoparticle may comprise two or more chemically distinct natural ligands attached to its surface, wherein at least one of the ligands is represented by the formula:

X-Sp-Z

(Wherein X, Sp and Z are as defined herein)

In certain embodiments, the nanoparticle may comprise two or more chemically distinct ligands attached to its surface, wherein the first ligand has the formula

N-Sp-Z

(Wherein, in the formula, N represents a primary amine group, a secondary amine group, an imidazole group, or an amide group)

The second ligand is represented by the formula:

Y-Sp-Z

Wherein Y represents a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group;

Sp and Z are as described herein, and each Sp and Z on the first ligand and the second ligand may be the same or different.

In certain embodiments, Z does not render the nanoparticles dispersible in a liquid medium comprising water.

The nanoparticles may be as described above and herein.

Preferred ligands include benzylphosphonic acid, benzylphosphonic acid containing at least one substituent in the ring of the benzyl group, a conjugate of such an acid, and mixtures comprising at least one of the foregoing. In certain embodiments, the ligand comprises 4-hydroxybenzylphosphonic acid, a pair of acids, and mixtures thereof. In certain embodiments, the ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate of an acid, or a mixture thereof.

Another preferred ligand comprises a ligand represented by the formula X-Sp-Z comprising an organic amine comprising a terminal hydroxyl group or a fluorinated organic amine.

According to another aspect of the present invention, a method of functionalizing nanoparticles is provided. The method comprises reacting a precursor to form nanoparticles having a predetermined composition in the presence of one or more chemically distinct ligands, wherein at least one of the ligands is represented by the formula:

X-Sp-Z

(Wherein,

X represents a primary amine group, a secondary amine group, an imidazole group, an amide group, a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group ; Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge; Z represents (i) a reactive group that not only can transfer specific chemical properties to the nanoparticles, but also provides specific chemical reactivity to the surface of the nanoparticles and / or (ii) a cyclic, halogenated and / or polar amphoteric group, In all cases Z is not reactive when exposed to light).

In certain embodiments, Z does not render the nanoparticles dispersible in a liquid medium comprising water.

In certain embodiments, the reactive group may comprise a functional, bifunctional or multifunctional reagent, and / or a reactive chemical group.

In certain embodiments, the cyclic group may include a saturated or unsaturated cyclic compound (including, but not limited to, a single ring, bi-cyclic structure, multi-cyclic structure, etc.) or an aromatic compound. In certain embodiments, the cyclic group may comprise one or more hetero-atoms. In certain embodiments, the cyclic group may include one or more substituents (including, but not limited to, reactive chemical groups, organic groups (alkyl, aryl, etc.), etc.). Other examples of cyclic groups are provided herein.

In certain embodiments, the halogenating group may include a fluorinating group, a perfluorinating group, a chlorinating group, a perchlorating group, a brominating group, a perbrominating group, an iodinating group, a periodating group and the like. Other examples of halogenating groups are provided herein.

In certain embodiments, the polar aprotic group may comprise a ketone, aldehyde, amide, urea, urethane or imine. Other examples of polar aprotic magnetic groups are provided herein.

In certain embodiments, the predetermined composition of nanoparticles comprises a semiconductor material.

In certain preferred embodiments, the predetermined composition comprises at least one metal and at least one chalcogen or phannicogen.

In certain embodiments, the precursor comprises at least one metal-containing precursor and at least one chalcogen-containing or phonitogen-containing precursor.

In certain embodiments, the nanoparticles may include a core comprising a first material and a shell (or coating material) disposed over at least a portion of the core surface and comprising a second material. In certain embodiments, the first material comprises a semiconductor material. In certain embodiments, the second material comprises a semiconductor material. In certain embodiments, one or more additional shells are disposed over at least a portion of the shell surface.

In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the semiconductor nanocrystals may include a core comprising a first material and a shell (or coating material) disposed over at least a portion of the core surface and comprising a second material. Preferably, the second material comprises a nanocrystalline semiconductor material. In certain embodiments, one or more additional shells are disposed over at least a portion of the shell surface.

Preferred ligands include benzylphosphonic acid, benzylphosphonic acid containing one or more substituents on the ring of the benzyl group, a conjugate of such an acid, and mixtures comprising at least one of the foregoing. In certain embodiments, the ligand comprises a 4-hydroxybenzylphosphonic acid, a conjugate of an acid, and a mixture comprising at least one of the foregoing. In certain embodiments, the ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate of an acid, or a mixture thereof.

Another preferred ligand comprises a ligand represented by the formula X-Sp-Z, including an organic amine or a fluorinated organic amine comprising a terminal hydroxyl group.

In certain embodiments, the precursor is reacted in the presence of at least two chemically distinct ligands, wherein at least one of the ligands is represented by the formula:

X-Sp-Z

Wherein X, Sp and Z are as described herein.

In certain embodiments, the precursor comprises at least one metal-containing precursor and at least one chalcogen-containing precursor or a phonitogen-containing precursor.

In certain embodiments, the precursor is reacted in the presence of at least two chemically distinct ligands, wherein the first ligand is a compound of formula

N-Sp-Z

(Wherein, in the formula, N represents a primary amine group, a secondary amine group, an imidazole group, or an amide group)

The second ligand is represented by the formula:

Y-Sp-Z

Wherein Y represents a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group;

Sp and Z are as described herein, and each Sp and Z on the first ligand and the second ligand may be the same or different.

In certain embodiments, the precursor comprises at least one metal-containing precursor and at least one chalcogen-containing precursor or a phonitogen-containing precursor.

According to another aspect of the present invention there is provided a method of overcoating at least a portion of the surface of a nanoparticle with a coating composition having a predetermined composition comprising contacting the precursor with a predetermined composition in the presence of one or more chemically distinct ligands Wherein at least one of the ligands is represented by the formula:

X-Sp-Z

Wherein X is selected from the group consisting of a primary amine group, a secondary amine group, an imidazole group, an amide group, a phosphone or arsonic group, a phosphine or arsinic acid group, a phosphate or arsenate group, Sp represents a spacer group, such as a group or an acceptor capable of transferring charge; Z is (i) capable of transferring a specific chemical property to the nanoparticle, as well as providing specific chemical reactivity to the surface of the nanoparticle A reactive group and / or (ii) a cyclic, halogenated and / or polar amphoteric group, where in all cases Z is not reactive upon exposure to light.

In certain embodiments, Z does not render the nanoparticles dispersible in a liquid medium comprising water.

In certain embodiments, the reactive group may comprise a functional, bifunctional or polyfunctional group and / or a reactive chemical group.

In certain embodiments, the cyclic group may include a saturated or unsaturated cyclic compound (including, but not limited to, a single ring, bi-cyclic structure, multi-cyclic structure, etc.) or an aromatic compound. In certain embodiments, the cyclic group may comprise one or more heteroatoms. In certain embodiments, the cyclic group may include one or more substituents (including, but not limited to, reactive chemical groups, organic groups (including alkyl, aryl, etc.)). Other examples of cyclic groups are provided herein.

In certain embodiments, the halogenating group may include a fluorinating group, a perfluorinating group, a chlorinating group, a perchlorating group, a brominating group, a perbrominating group, an iodinating group, a periodating group and the like. Other examples of halogenating groups are provided herein.

In certain embodiments, the polar aprotic group may comprise a ketone, aldehyde, amide, urea, urethane or imine. Other examples of polar aprotic magnetic groups are provided herein.

In certain embodiments, the nanoparticles comprise a semiconductor material.

In certain embodiments, the nanoparticles may comprise a core comprising a first material and a shell (or coating material) disposed over at least a portion of the core surface and comprising a second material. In certain embodiments, the first material comprises a semiconductor material. In certain embodiments, the second material comprises a semiconductor material. In certain embodiments, one or more additional shells are disposed over at least a portion of a surface of the shell.

In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the semiconductor nanocrystals may comprise a core comprising a first material and a shell (or coating material) disposed over at least a portion of a surface of the core and comprising a second material. Preferably, the second material comprises a nanocrystalline semiconductor material. In certain embodiments, the at least one additional shell is disposed over at least a portion of the shell surface.

In certain embodiments, the predetermined composition of the coating material comprises a semiconductor material, preferably a nanocrystalline semiconductor material.

In certain preferred embodiments, the predetermined composition comprises at least one metal and at least one chalcogen or phannicogen.

In certain embodiments, the precursor comprises at least one metal-containing precursor and at least one chalcogen-containing or phonitogen-containing precursor.

Preferred ligands include benzylphosphonic acid, benzylphosphonic acid containing one or more substituents on the ring of the benzyl group, a conjugate of such an acid, and a mixture of one or more of the foregoing. In certain embodiments, the ligand comprises 4-hydroxybenzylphosphonic acid, a pair of acids, and mixtures thereof. In certain embodiments, the ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate of an acid, or a mixture thereof.

Another preferred ligand comprises a ligand represented by the formula X-Sp-Z comprising an organic amine comprising a terminal hydroxyl group or a fluorinated organic amine.

In certain embodiments, the precursor is reacted in the presence of at least two chemically distinct ligands, and at least one of the ligands is represented by the formula:

X-Sp-Z

Wherein X, Sp and Z are as described herein.

In certain embodiments, the precursor is reacted in the presence of at least two chemically distinct ligands, wherein the first ligand is a compound of formula

N-Sp-Z

(Wherein, in the formula, N represents a primary amine group, a secondary amine group, an imidazole group, or an amide group)

The second ligand is represented by the formula:

Y-Sp-Z

Wherein Y represents a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group;

Sp and Z are as described herein, and each Sp and Z on the first ligand and the second ligand may be the same or different.

In another aspect of the invention, a mixture comprising a liquid medium and a semiconductor material precursor is reacted with a first ligand compound comprising an amine group (e.g., N-Sp-Z, wherein N is a primary amine group, , An imidazole group, an amide group) and a second ligand compound comprising an acid group (e.g., Y-Sp-Z, where Y is a phosphone or arsonic acid group, a phosphine or arsinic acid group, Or an arsenate group, a phosphine or an arsine oxide group) in the presence of at least one compound selected from the group consisting of a metal compound and a metal compound. Sp and Z are as described herein.

In certain preferred embodiments, a first ligand compound comprising an amine group and a second ligand compound comprising an acid group are initially present in equimolar amounts, an equimolar amount is determined by the amine group content of the first ligand compound and the acid of the second ligand compound Is determined based on the content of the base.

In certain embodiments, the first ligand compounds is represented by the formula AL (a group formula, A is the acid, L is also an aryl group, a heteroaryl group or a straight-chain or branched-chain C _{1 -18} comprising the hydrocarbon chain). In certain embodiments, the second ligand compound is represented by the formula NL, wherein N is an amine group and L is an aryl group, a heteroaryl group, or a straight or branched chain C _1-18 hydrocarbon chain. In certain embodiments, the hydrocarbon chain comprises one or more double bonds, one or more triple bonds or one or more double bonds and one triple bond. In certain embodiments, the hydrocarbon chains are _{-O-, -S-, -N (R a} ) -, -N (R a) -C (O) -O-, -OC (O) -N (R a) _{-, -N (R a) -C} (O) -N (R b) -, -OC (O) -O-, -P (R a) - or _{-P (O) (R a)} - ( where Wherein each R _a and R _b is independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyl or haloalkyl. In certain embodiments, the aryl group is a substituted or unsubstituted cyclic aromatic group. In certain embodiments, the aryl group includes phenyl, benzyl, naphthyl, tolyl, anthracyl, nitrophenyl, or halophenyl. In certain embodiments, the heteroaryl group includes aryl groups having one or more heteroatoms in the ring, such as furyl, pyridyl, pyrrolyl, phenanthryl. In certain embodiments, A comprises a phosphinic acid group or a carboxylic acid group. In certain embodiments, A comprises an oleic acid group or a myristic acid group. In certain preferred embodiments, A comprises a phosphonic acid group.

In certain embodiments of the methods described herein, the method is performed in a liquid medium. Preferably, the liquid medium comprises a coordination solvent or a mixture of coordination solvents. Examples of coordination solvents include those provided herein. Other coordination solvents may also be used. In certain embodiments, the method may be carried out in a liquid medium comprising a non-coordinating solvent or a mixture of non-coordinating solvents. Examples of non-coordinating solvents include, but are not limited to, squalane, octadecane, or other saturated hydrocarbon molecules. Mixtures of two or more solvents may also be used. Other suitable non-coordination solvents may be readily ascertainable by those skilled in the art.

In particular aspects and embodiments of the present invention, which are described or contemplated in the following description, the following detailed description, and the claims, nanoparticles may include a core and an overcoat (also referred to herein as a shell). Nanoparticles comprising a core and a shell are referred to as having a core / shell structure. The shell is disposed over at least a portion of the core. In certain embodiments, the shell is disposed on all or substantially all of the outer surface of the core. In certain embodiments of nanoparticles comprising a core / shell structure, the core may comprise a first semiconductor material and the shell may comprise a second semiconductor material. In certain embodiments, the core comprises semiconductor nanocrystals. In certain embodiments, the nanocrystals may have a diameter of less than about 10 nanometers. In embodiments involving multiple nanoparticles, the distribution of nanoparticle sizes is preferably monodisperse.

In certain aspects and embodiments of the invention described and / or contemplated in the following description, the following detailed description, and the claims, the nanoparticles are either water insoluble or non-dispersible in a liquid medium comprising water.

In certain aspects and embodiments of the invention described or contemplated in the foregoing description, the following detailed description, and the claims, it is to be understood that nanoparticles (preferably semiconductor nanocrystals) comprising a semiconductor material may comprise one or more ligands RTI ID = 0.0 > at least < / RTI > In certain embodiments, the coating comprises one or more materials. In certain embodiments involving a coating comprising one or more materials, the material is applied continuously. In certain embodiments, the core may comprise a plurality of overcoats or shells disposed on the surface thereof. Each of the plurality of overcoats or shells may comprise the same or different composition. In certain aspects and embodiments of the invention described or contemplated by the following description, the following detailed description, and the claims, the method is performed in a non-aqueous medium. In certain preferred embodiments, the method is a colloid synthesis method.

These and other aspects and embodiments described herein constitute an embodiment of the present invention.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed. Other embodiments will be apparent to those skilled in the art in light of the practice of the invention as set forth herein and in the appended claims.

In the drawings,
Figure 1 illustrates the chemical structure of a particular example composition useful in practicing the present invention.
Figure 2 shows an atomic force microscope image showing 5 nm CBP thermally vaporized on an aliphatic ligand quantum dot layer.
Figure 3 shows an atomic force microscope image showing 15 nm CBP thermally vaporized on an aliphatic ligand quantum dot layer.
Figure 4 shows an atomic force microscope image showing 5 nm CBP thermally evaporated over an aromatic ligand quantum dot layer.
5 shows an atomic force microscope image showing the effect of the ligand composition on the interface shape of the semiconductor nanocrystal layer.
Figure 6 shows an example of the chemical structure of a particular composition useful for carrying out the invention.
Figure 7 shows an example of the chemical structure of a particular composition useful for carrying out the present invention.
Fig. 8 shows a spectrum for illustrating a method for measuring quantum efficiency.
The accompanying drawings are merely provided for illustration purposes only and the actual structure may be different in many respects including, for example, relative evaluation criteria, etc. [
BRIEF DESCRIPTION OF THE DRAWINGS For a better understanding of the present invention, together with other advantages and capabilities thereof, reference is made to the disclosure of the present specification and the appended claims in conjunction with the above described drawings.

According to a particular embodiment of the invention there is provided a nanoparticle comprising a ligand attached to its surface, wherein the ligand is represented by the formula:

X-Sp-Z

Wherein X is a group selected from the group consisting of a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group, a phosphone or arsonic group, a phosphine or arsinic acid group, , A phosphine or an arsine oxide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group that (i) not only can transfer specific chemical properties to the nanoparticles, but also provides specific chemical reactivity to the surface of the nanoparticles and / or (ii) represents a cyclic, halogenated or polar aprotic group. The ligand is attached or coordinated to the surface of the nanoparticle during its formation or overcoating.

Examples of Sp include, but are not limited to, linear or branched C ₁ -C ₁₈ hydrocarbon chains. In certain embodiments, the hydrocarbon chain comprises one or more double bonds, one or more triple bonds, or one or more double bonds and one triple bond. In certain embodiments, the hydrocarbon chains are _{-O-, -S-, -N (R a} ) -, -N (R a) -C (O) -O-, -OC (O) -N (R a) _{-, -N (R a) -C} (O) -N (R b) -, -OC (O) -O-, -P (R a) - or _{-P (O) (R a)} - ( where Wherein each R _a and R _b is independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxyalkyl, hydroxyl or haloalkyl.

Examples of reactive groups include, without limitation, functional, bifunctional and multifunctional reagents (e.g., homobifunctional or heterobifunctional), and reactive chemical groups (e.g., thiol or carboxyl, hydroxyl, amino , Amines, sulfo, etc.). Examples of further reactive groups include carbodithioates, carbodithioic acids, thioureas, amides, phosphine oxides, phosphones or phosphinic acids, thiophosphones or thiophosphinic acids, which are perhalogenated or partially halogenated Alkyl and / or aryl units. Examples of cyclic groups include, but are not limited to, saturated or unsaturated cyclic or bicyclic compounds (e.g., cyclohexyl, isobornyl, etc.) or aromatic compounds (e.g., phenyl, benzyl, Biphenyl, fluorenyl, triarylamine, and the like). In certain embodiments, cyclic groups may include one or more substituents (including, but not limited to, reactive chemical groups, organic groups (such as alkyl, aryl, etc.), and the like. The halogenating group includes, but is not limited to, a fluorinating group, a perfluorinated group (e.g., perfluoroalkyl, perfluorophenyl, perfluoroamine, etc.), a chlorinating group, and a perchlorinating group. Examples of polar aprotic magnetic groups include, but are not limited to, ketones, aldehydes, amides, ureas, urethanes, imines, and the like.

In certain embodiments, the group comprising Z imparts a predetermined chemical miscibility property to the semiconductor nanocrystals to which it is attached.

In certain embodiments, Z does not include non-functionalized linear or branched C ₁ -C ₁₈ hydrocarbon chains.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals.

According to a particular embodiment, there is provided a nanoparticle comprising two or more chemically distinct ligands attached to its surface, wherein at least one of said ligands is represented by the formula:

X-Sp-Z

Wherein X is a group selected from the group consisting of a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group, a phosphone or arsonic group, a phosphine or arsinic acid group, , A phosphine or an arsine oxide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group that (i) not only can transfer certain chemical properties to the nanocrystals but also provides specific chemical reactivity to the surface of the nanocrystals and / or (ii) represents a cyclic, halogenated or polar aprotic group.

Examples of Sp and Z include, but are not limited to, those described herein.

In certain embodiments, Z does not include non-functionalized linear or branched C ₁ -C ₁₈ hydrocarbon chains.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals.

According to a particular embodiment, there is provided a nanoparticle comprising two or more chemically distinct ligands attached to the surface thereof, wherein the first ligand is represented by the following formula

N-Sp-Z

(Wherein N represents a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group or other nitrogen-containing functional group,

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group capable of transferring specific chemical properties to the nanocrystal and / or providing specific chemical reactivity to the surface of the nanocrystal)

The second ligand is represented by the formula:

Y-Sp-Z

(Wherein,

Y represents a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group, or other phosphorus-containing or arsenic-containing functional groups;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group capable of transferring specific chemical properties to the nanocrystal and / or providing specific chemical reactivity to the surface of the nanocrystal.

Examples of Sp and Z for inclusion in N-Sp-Z and P-Sp-Z include those described herein without limitation. Sp and Z may be independently selected. Sp and Z contained in each of the two ligands may be the same or different.

In certain embodiments, Z does not include non-functionalized linear or branched C ₁ -C ₁₈ hydrocarbon chains.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals.

According to another embodiment of the present invention, a method of functionalizing nanoparticles is provided. The method comprises reacting a precursor to form a nanoparticle having a predetermined composition in the presence of the ligand X-Sp-Z described herein, wherein X, Sp and Z are as described herein.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the predetermined precursor comprises a metal-containing precursor and a chalcogen-containing or phonitogen-containing precursor. The precursor is preferably included in the reaction mixture in an amount based on a predetermined composition.

In certain embodiments, the method is performed in a liquid medium. Preferably, the liquid medium comprises a coordination solvent or a mixture of coordination solvents. Examples of coordination solvents include those provided herein. Other coordination solvents may also be used. In certain embodiments, the method can be performed in a liquid medium comprising a non-coordinating solvent or a mixture of non-coordinating solvents. Examples of non-coordinating solvents include, but are not limited to, squalane, octadecane, or other saturated hydrocarbon molecules. Mixtures of two or more solvents may also be used. Other suitable non-coordination solvents may be readily ascertainable by those skilled in the art.

In certain embodiments, the molar ratio of the total moles of metal contained in one or more metal-containing precursors to the total moles of ligands represented by the formula X-Sp-Z ranges from about 1: 0.1 to about 1: 100. In certain embodiments, the molar ratio of the total moles of metal contained in one or more metal-containing precursors to the total moles of ligands represented by the formula X-Sp-Z ranges from about 1: 1 to about 1: 50. In certain embodiments, the molar ratio of the total moles of metals contained in the at least one metal-containing precursor to the total moles of ligands represented by the formula X-Sp-Z ranges from about 1: 1 to about 1:30. In certain embodiments in which the process is carried out in a liquid medium, the molar ratio of the total moles of liquid medium to the total moles of ligand represented by the formula X-Sp-Z ranges from about 500: 1 to about 2: 1. In certain embodiments, the molar ratio of the total moles of liquid medium to the total moles of ligand represented by the formula X-Sp-Z is from about 100: 1 to about 5: 1. In certain embodiments, the molar ratio of the total moles of ligand media to the total moles of ligands represented by the formula X-Sp-Z ranges from about 50: 1 to about 5: 1.

According to certain embodiments, a method of functionalizing nanoparticles is provided. The method includes reacting a precursor to form nanoparticles having a predetermined composition in the presence of at least two chemically distinct ligands, wherein at least one of the ligands is represented by the formula:

X-Sp-Z

(Wherein,

X is a group selected from the group consisting of a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group, a phosphone or arsonic acid group, a phosphine or arsine acid group, a phosphate or arsenate group, An arsine oxide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group that (i) not only can transfer certain chemical properties to the nanoparticles, but also provides specific chemical reactivity to the surface of the nanocrystals and / or (ii) represents a cyclic, halogenated or polar aprotic group.

In certain embodiments, Z does not include non-functionalized linear or branched C ₁ -C ₁₈ hydrocarbon chains. Examples of Sp and Z include, but are not limited to, those described herein.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the predetermined precursor comprises a metal-containing precursor and a chalcogen-containing or phonitogen-containing precursor. The precursor is preferably included in the reaction mixture in an amount based on a predetermined composition.

In certain embodiments, a method of functionalizing nanoparticles is provided. The method comprises reacting a precursor to form a nanoparticle having a predetermined composition in the presence of at least two chemically distinct ligands, wherein the first ligand is represented by the following formula

N-Sp-Z

(Wherein,

N represents a primary amine group, a secondary amine group, urea, thiourea, an imidazole group, or an amide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group not only capable of transferring specific chemical properties to the nanocrystals but also providing specific chemical reactivity to the surface of the nanocrystals)

The second ligand is represented by the formula:

Y-Sp-Z

(Wherein,

Y represents a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group capable of delivering specific chemical properties to the nanocrystals as well as providing specific chemical reactivity to the surface of the nanocrystals.

Examples of Sp and Z include, but are not limited to, those described herein. Sp and Z may be independently selected. Sp and Z contained in each of the two ligands may be the same or different.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the predetermined precursor comprises a metal-containing precursor and a chalcogen-containing or phonitogen-containing precursor. The precursor is preferably included in the reaction mixture in an amount based on a predetermined composition. According to another embodiment of the present invention, there is provided a method of overcoating at least a portion of the surface of a nanoparticle with a coating material having a predetermined composition, the method comprising the step of coating the ligand represented by the formula X-Sp-Z and the coated nanoparticle Reacting a precursor for a predetermined coating material in the presence of a solvent, wherein X, Sp and Z are as described herein. In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the coating composition comprises a semiconductor material. In certain embodiments, the precursor comprises a metal-containing precursor and a chalcogen-containing or phonitogen-containing precursor. The precursor is preferably included in the reaction mixture in an amount based on a predetermined composition.

In certain embodiments, the method is performed in a liquid medium. Preferably, the liquid medium comprises a coordination solvent or a mixture of coordination solvents. Examples of coordination solvents include those provided herein. Other coordination solvents may also be used. In certain embodiments, the method may be carried out in a liquid medium comprising a non-coordinating solvent or a mixture of non-coordinating solvents. Examples of non-coordinating solvents include, but are not limited to, squalane, octadecane, or other saturated hydrocarbon molecules. Mixtures of two or more solvents may also be used. Other suitable non-coordination solvents may be readily ascertainable by those skilled in the art.

In certain embodiments, the molar ratio of the total moles of metal contained in the overcoated nanoparticles to the total moles of ligands represented by the formula X-Sp-Z ranges from about 1: 0.1 to about 1: 100. In certain embodiments, the molar ratio of the total moles of metal contained in the overcoated nanoparticles to the total moles of ligands represented by the formula X-Sp-Z ranges from about 1: 1 to about 1: 50. In certain embodiments, the molar ratio of the total moles of metal contained in the nanoparticles to the total moles of ligands represented by the formula X-Sp-Z ranges from about 1: 1 to about 1:30.

In certain embodiments of the method carried out in a liquid medium, the molar ratio of the total moles of liquid medium to the total moles of ligand represented by the formula X-Sp-Z ranges from about 500: 1 to about 2: 1. In certain embodiments, the molar ratio of the total moles of liquid medium to the total moles of ligand represented by the formula X-Sp-Z ranges from about 100: 1 to about 5: 1. In certain embodiments, the molar ratio of the total moles of liquid medium to the total moles of ligand represented by the formula X-Sp-Z ranges from about 50: 1 to about 5: 1. According to a further embodiment of the present invention there is provided a method of overcoating at least a portion of the surface of a nanoparticle with a coating material having a predetermined composition, the method comprising the step of providing the presence of at least two chemically distinct ligands and nanoparticles to be coated , Wherein at least one of said ligands is represented by the formula: < RTI ID = 0.0 >

X-Sp-Z

(Wherein,

X is a group selected from the group consisting of a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, an amide group, a phosphone or arsonic acid group, a phosphine or arsine acid group, a phosphate or arsenate group, An arsine oxide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group that (i) not only can transfer certain chemical properties to the nanocrystals but also provides specific chemical reactivity to the surface of the nanocrystals and / or (ii) represents a cyclic, halogenated or polar aprotic group.

In certain embodiments, Z does not include non-functionalized linear or branched C ₁ -C ₁₈ hydrocarbon chains.

Examples of Sp and Z include, but are not limited to, those described herein.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. In certain embodiments, the coating composition comprises a semiconductor material. In certain embodiments, the precursor comprises a metal-containing precursor and a chalcogen-containing or phonitogen-containing precursor. The precursor is preferably included in the reaction mixture in an amount based on a predetermined composition.

In certain embodiments, there is provided a method of overcoating at least a portion of the surface of a nanoparticle with a coating material having a predetermined composition, the method comprising the step of coating a predetermined coating material in the presence of two or more chemically distinct ligands and coated nanoparticles Wherein the first ligand is selected from the group consisting of the following formula

N-Sp-Z

(Wherein N represents a primary amine group, a secondary amine group, a urea, a thiourea, an imidazole group, or an amide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group not only capable of transferring specific chemical properties to the nanocrystals but also providing specific chemical reactivity to the surface of the nanocrystals)

The second ligand is represented by the formula:

Y-Sp-Z

Wherein Y represents a phosphone or arsonic acid group, a phosphine or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group;

Sp represents a spacer group, e.g., a group or an isomer capable of transferring charge;

Z represents a reactive group capable of transferring specific chemical properties to the nanocrystals as well as providing specific chemical reactivity to the surface of the nanocrystals.

Examples of Sp and Z include, but are not limited to, those described herein. Sp and Z may be independently selected. Sp and Z comprising two ligands may be the same or different.

In certain embodiments, the nanoparticles comprise semiconductor nanoparticles. In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals.

In certain embodiments, the coating composition comprises a semiconductor material. In certain embodiments, the precursor comprises a metal-containing precursor and a chalcogen-containing or phonitogen-containing precursor. The precursor is preferably included in the reaction mixture in an amount based on a predetermined composition.

In carrying out the method described herein, the precursor is selected and reacted for a time therefor for an amount therefor under reaction conditions to produce nanoparticles with a predetermined composition. Such variables can be readily determined by those skilled in the art. In certain embodiments, the reaction is carried out in a controlled atmosphere (substantially free of moisture and air). In certain preferred embodiments, the reaction is carried out in a no-water-inert atmosphere.

In certain embodiments of the invention, nanoparticles (e.g., semiconductor nanocrystals) are formed or overcoated to produce a shell on at least a portion of the outer surface of the nanoparticle in the presence of one or more molecules having the formula:

(Wherein,

R ₁ represents a hydroxyl group; R ₂ is selected from the group consisting of hydroxyl, hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₁₁ , -NHR ₁₁ , -NR ₁₁ R ₁₁ , -SR ₁₁ wherein R ₁₁ is hydrogen, R ₃ and R ₄ may be the same or different and each represents a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,

(Wherein R ₁₂ is an alkyl or alkylene group or an aryl or arylene group); R ₅ is in the hydrogen, alkyl group containing at least one functional group, an alkylene group, an aryl or arylene _{group, -OR 13, -NHR 13, -NR} 13 R 13, -SR 13 ( where, R ₁₃ is hydrogen, An alkyl group or an aryl group; R ₆ represents hydrogen; Wherein R ₇ represents hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₁₄ , -NHR ₁₄ , -NR ₁₄ R ₁₄ , -SR ₁₄ (wherein R ₁₄ represents hydrogen, an alkyl group or an aryl group) Lt; / RTI > R ₈ and R ₉ may be the same or different and each represents a bond, an alkylene group, an aryl or arylene group, a fluorocarbon group,

(Wherein R < ₁₅ > is an alkyl or alkylene group or an aryl or arylene group); R ₈ also represents an alkyl group; R ₉ may represent an alkyl group containing at least one functional group; R ₁₀ is hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₁₆ , -NHR ₁₆ , -NR ₁₆ R ₁₆ , -SR ₁₆ (Wherein R ₁₆ represents hydrogen, an alkyl group or an aryl group).

The configuration described herein also opens up the possibility of a unit-of-synthesis synthesis scheme to match the quantum dot surface with desired features. For example, the terminal hydroxyl groups provide sites for additional chemical reactivity. The nucleophilic nature of the -OH group can carry out various addition and substitution reactions with suitable electrophiles. For example, the following ester and urethane linkages can be obtained by reacting proton dyes (e. G., Semiconductor nanocrystals) with such nucleophilic surface groups with an electrophile such as an acid chloride, isocyanate, or carboxylic acid group:

Here, R may be any substituent. The -OH group can displace the primary amine and as a result an amide and urea bond with the electrophilic moiety mentioned here is obtained:

Here, R may be any substituent.

Functionalization of surface of semiconductor nanocrystals with terminal hydroxyl groups

Chemical structure used:

Dimethylimidazolidone (DMI), carbitol acetate, N, N-dimethyl acrylamide (DMAc), or the like, in the presence of phosphine oxide (TOPO) in a high boiling polar aprotic solvent ), 1-methyl-2-pyrrolidinone (NMP), etc.) can be added to achieve this approach.

Examples of binding species to hydroxy-terminated semiconductor nanocrystals

The functional groups are isocyanate, acid chloride, and carboxylic acid from left to right. Here, R may be any of the following chemical species, but is not limited thereto (having any length of aliphatic chain linker linking the molecule to the functional groups indicated herein).

The systems described herein can be further extended by forming similar variants to the phosphine oxide derivatives used as solvents in the overcoating procedure. Such species have the formula:

Here, R ₁₇ , R ₁₈ and R ₁₉ may be the same or different and each represents a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,

(Wherein R < ₂₃ > is an alkyl or alkylene group or an aryl or arylene group); R ₂₀ , R ₂₁ and R ₂₂ may be the same or different and are selected from the group consisting of hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₂₄ , -NHR ₂₄ , -NR ₂₄ R ₂₄ , -SR ₂₄ , And R ₂₄ represents hydrogen, an alkyl group or an aryl group.

In order to avoid the introduction of impurities which may have an unpredictable effect on the reaction, the ligand should preferably have a purity of at least 99% by weight, preferably more than 99.5% by weight.

The phosphine or arginic acid groups useful in the practice of the present invention may also include mono- and di-phosphine / arsinic acid groups.

According to a particular embodiment of the present invention, nanoparticles (e. G., Semiconductors < / RTI > Nanocrystals) are formed or overcoated:

(In the above left formula, P may alternatively be As)

Wherein R ₁ represents a hydroxyl group; R ₂ is hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₁₁ , -NHR ₁₁ , -NR ₁₁ R ₁₁ , -SR ₁₁ wherein R ₁₁ represents a hydrogen, an alkyl group or an aryl group, ; R ₃ and R ₄ may be the same or different and each represents a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,

(Wherein R ₁₂ is an alkyl or alkylene group or an aryl or arylene group); R ₅ is hydrogen, an alkyl group, an alkylene group containing one or more functional groups, aryl or arylene _{group, -OR 13, -NHR 13, -NR} 13 R 13, -SR 13 ( At this time, R ₁₃ is hydrogen, alkyl Or an aryl group; R ₆ represents hydrogen; R ₇ is selected from the group consisting of hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₁₄ , -NHR ₁₄ , -NR ₁₄ R ₁₄ , -SR ₁₄ wherein R ₁₄ is hydrogen, an alkyl group or an aryl group ; R ₈ and R ₉ may be the same or different and each represents a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,

(Wherein R < ₁₅ > is an alkyl or alkylene group or an aryl or arylene group); R ₁₀ is hydrogen, an alkyl group containing at least one functional group, an alkylene group, an aryl or arylene group, -OR ₁₆ , -NHR ₁₆ , -NR ₁₆ R ₁₆ , -SR ₁₆ wherein R ₁₆ is hydrogen, Group or an aryl group).

As mentioned herein, the system can be further extended by forming a similar variability to the phosphine oxide derivative used as solvent in the overcoating procedure. Such species have the formula:

Here, R ₁₇ , R ₁₈ and R ₁₉ may be the same or different and each represents a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,

(Wherein R < ₂₃ > is an alkyl or alkylene group or an aryl or arylene group); R ₂₀ , R ₂₁ and R ₂₂ may be the same or different and are selected from the group consisting of hydrogen, an alkyl or alkylene group, an aryl or arylene group, -OR ₂₄ , -NHR ₂₄ , -NR ₂₄ R ₂₄ , -SR ₂₄ , And R ₂₄ represents hydrogen, an alkyl group or an aryl group.

In order to avoid the introduction of impurities which may have an unpredictable effect on the reaction, the ligand should preferably have a purity of at least 99% by weight, preferably more than 99.5% by weight.

Phosphinic acid groups useful in the practice of the present invention may include mono- and di-phosphinic acid groups.

As described herein, arsenic modification of the phosphorus-containing acid and oxide groups described above may also be used.

The present invention will become more apparent from the following examples, which are to be construed as examples of the present invention.

<Examples>

Example  1A

The overcoating procedure is carried out with TOPO as a solvent and conventional aliphatic phosphonic acids and amine species are replaced with aromatic derivatives (see Fig. 1) to obtain semiconductor nanocrystals with new surface chemistry while maintaining their optical properties. Semiconductor nanocrystals are no longer soluble in hexane, but are readily soluble in toluene and chloroform. In addition, a thin film of organic molecules can be reliably deposited on an ordered film of synthetic modified nanocrystals, without "puddling" associated with conventional aliphatic semiconductor nanocrystal surface chemistry (see FIGS. 2-5). Despite the fact that TOPO is exceeded during the reaction, it is believed that the phosphonic acid / amine salt is the predominant species on the surface of the semiconductor nanocrystals.

Manufacture of aromatic semiconductor nanocrystals capable of emitting red light

Synthesis of CdSe core : 1 mmol of cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine at 100 &lt; 0 &gt; C in a 20 mL vial followed by drying and degassing for 1 hour. 15.5 millimoles of trioctylphosphine oxide and 2 millimoles of octadecylphosphonic acid were added to a three-necked flask, dried and degassed at 140 DEG C for 1 hour. After degassing, the Cd solution was added to the oxide / acid flask and the mixture was heated to 270 &lt; 0 &gt; C under nitrogen. Once the temperature reached 270 DEG C, 8 millimoles of tri-n-butylphosphine was injected into the flask. 1.1 mL of 1.5M TBP-Se was rapidly injected and the temperature was again returned to 270 占 폚. The reaction mixture was heated at 270 &lt; 0 &gt; C for 15-30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe core was precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 3: 1 mixture of methanol and isopropanol. The isolated core was then dissolved in hexane and used to make the core-shell material.

Synthesis of CdSe / CdZnS core-shell nanocrystals : 25.86 millimoles of trioctylphosphine oxide and 2.4 millimoles of benzylphosphonic acid were loaded into a four-necked flask. The mixture was dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was then cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdSe core was added to the reaction mixture. The hexane was removed under reduced pressure, and 2.4 mmol of phenylethylamine was added to the reaction mixture. Dimethylcadmium, diethylzinc, and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. While Cd and Zn were mixed in equimolar proportions, S was 2-fold excess for Cd and Zn. The Cd / Zn and S samples were each dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 155 캜 under nitrogen. The precursor solution was added dropwise at 155 &lt; 0 &gt; C over 2 hours using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by addition of a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in toluene. The semiconductor nanocrystals had a maximum emission of 616 nm with FWHM of 34 nm and a solution quantum yield of 50%.

Sample preparation . The cleaned glass substrate was ashed in a plasma cleaner and coated with PEDOT: PSS (70 nm). The substrate was placed in a nitrogen atmosphere and fired at 120 ° C for 20 minutes. 50 nm E105 (N, N'-bis (3-methylphenyl) -N, N'-bis- (phenyl) -9,9- spiro-bifluorene, LumTec) And evaporated in a vacuum chamber. Application of aromatic quantum dots was achieved through contact printing. The dispersion of semiconductor nanocrystals with an optical density (OD) of 0.3 in the first absorption characteristic was spin-coated in a parylene-coated stamp at 3000 rpm for 60 seconds and then spotted onto an E105 substrate to deposit a monolayer of aromatic quantum dots . Subsequently, the substrate was brought back to the thermal evaporation chamber and CBP (4,4'-bis (carbazol-9-yl) biphenyl, LumTec) of 5 nm and 15 nm, respectively, was evaporated below 2e-6 torr. Figs. 2 to 5 show images of the samples described in this sample preparation example.

The following Examples 1-B and 1-C relate to the production of semiconductor nanocrystals comprising a benzylphosphonic acid ligand, without using the phenylethylamine shown in Fig.

Example  1-B

Production of semiconductor nanocrystals capable of emitting green light:

Synthesis of ZnSe core : 0.69 mmol of diethylzinc was dissolved in 5 mL of tri-n-octylphosphine and mixed with 1 mL of 1M TBP-Se. 28.9 mmol of oleylamine was loaded into a three-necked flask, dried and degassed at 90 DEG C for 1 hour. After degassing, the flask was heated to 310 DEG C under nitrogen. Once the temperature reached 310 캜, a Zn solution was injected and the reaction mixture was heated at 270 캜 for 15 to 30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 350 nm, the reaction was stopped by dropping the flask temperature to 160 캜 and used without further purification for the preparation of the CdZnSe core.

Synthesis of CdZnSe core : 1.12 mmol dimethylcadmium was dissolved in 5 mL of tri-n-octylphosphine and mixed with 1 mL of 1M TBP-Se. A four-necked flask was charged with 41.38 mmol of trioctylphosphine oxide and 4 mmol of hexylphosphonic acid, dried and degassed at 120 ° C for 1 hour. After degassing, the oxide / acid was heated to 160 ° C under nitrogen and the Cd / Se solution was added via syringe pump over 20 minutes immediately after 8 ml of the ZnSe core growth solution was transferred to the flask at 160 ° C. The reaction mixture was heated at 150 &lt; 0 &gt; C for 16-20 hours while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the emission peak of the nanocrystals reached 500 nm, the reaction was stopped by cooling the mixture to room temperature. CdZnSe cores were precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 2: 1 mixture of methanol and n-butanol. The isolated core was dissolved in hexane and used to form the core-shell material.

Synthesis of CdZnSe / CdZnS core-shell nanocrystals : 25.86 millimoles of trioctylphosphine oxide and 2.4 millimoles of benzylphosphonic acid were loaded into a four-necked flask. The mixture was then dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdZnSe core was added to the reaction mixture. Hexane was removed under reduced pressure. Dimethylcadmium, diethylzinc, and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. While Cd and Zn were mixed in equimolar proportions while S was 2-fold excess for Cd and Zn. Cd / Zn and S samples were respectively dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 150 캜 under nitrogen. The precursor solution was added dropwise at 150 &lt; 0 &gt; C over 1 hour using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in hexane and used to form semiconductor nanocrystalline composites.

Example  1-C

Manufacture of semiconductor nanocrystals capable of emitting red light

Synthesis of CdSe core : 1 mmol of cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine at 100 &lt; 0 &gt; C in a 20 mL vial followed by drying and degassing for 1 hour. 15.5 millimoles of trioctylphosphine oxide and 2 millimoles of octadecylphosphonic acid were added to a three-necked flask, dried and degassed at 140 DEG C for 1 hour. After degassing, the Cd solution was added to the oxide / acid flask and the mixture was heated to 270 &lt; 0 &gt; C under nitrogen. Once the temperature reached 270 DEG C, 8 millimoles of tri-n-butylphosphine was injected into the flask. The temperature was returned to 270 캜 and 1.1 mL of 1.5 M TBP-Se was rapidly injected. The reaction mixture was heated at 270 &lt; 0 &gt; C for 15-30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe core was precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 3: 1 mixture of methanol and isopropanol. The isolated core was dissolved in hexane and used to form the core-shell material.

Synthesis of CdSe / CdZnS core-shell nanocrystals : 25.86 millimoles of trioctylphosphine oxide and 2.4 millimoles of benzylphosphonic acid were loaded into a four-necked flask. The mixture was then dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdSe core was added to the reaction mixture. The hexane was removed under reduced pressure. Dimethylcadmium, diethylzinc, and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. While Cd and Zn were mixed in equimolar proportions while S was 2-fold excess for Cd and Zn. Cd / Zn and S samples were respectively dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 155 DEG C under nitrogen. The precursor solution was added dropwise at 155 &lt; 0 &gt; C over 2 hours using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in toluene and used to form a quantum dot composite.

Example  2

The overcoating procedure was performed with TOPO as the solvent and the fluorinated derivative of the amine species was used with hexylphosphonic acid, aliphatic phosphonic acid (see FIG. 6). After the reaction, these semiconductor nanocrystals were no longer dissolved in conventional organic solvents such as hexane, toluene, chloroform, methylene chloride and the like. However, the samples were soluble in fluorinated solvents such as perfluorohexane, perfluorotoluene and Fluorinert (FC-77). Fluorination levels can be enhanced by the use of fluorinated amines in conjunction with fluorinated phosphonic acid derivatives and / or fluorinated TOPO equivalents.

Fluorinating the surface of semiconductor nanocrystals can promote deposition of materials in a variety of applications. Since the fluorinated solvent is unable to solvate the organic transfer material, the fluorinated semiconductor nanocrystals have been successfully spin-cast directly onto the organic thin film.

Example  3

An overcoating procedure was performed with TOPO as the solvent and hexylphosphonic acid was provided to the amine species functionalized with terminal hydroxyl groups (see FIG. 7). After the reaction, the sample was not dissolved in hexane or toluene but dissolved in a polar solvent such as methanol and isopropanol. Again, the polarity of the semiconductor nanocrystal surface can be enhanced by using an amine with an alkyl or arylphosphonic acid having a terminal hydroxyl group and / or using an alkyl or aryl phosphine oxide having a terminal hydroxyl group.

Example  4

Manufacture of semiconductor nanocrystals capable of emitting red light

Synthesis of CdSe core : 1 mM cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine in a 20 mL vial at 100 &lt; 0 &gt; C, then dried and degassed for 1 hour. 15.5 millimoles of trioctylphosphine oxide and 2 millimoles of octadecylphosphonic acid were added to a three-necked flask, dried and degassed at 140 DEG C for 1 hour. After degassing, the Cd solution was added to the oxide / acid flask and the mixture was heated to 270 &lt; 0 &gt; C under nitrogen. Once the temperature reached 270 DEG C, 8 millimoles of tri-n-butylphosphine was injected into the flask. The temperature was returned to 270 캜 and 1.1 mL of 1.5 M TBP-Se was rapidly injected. The reaction mixture was heated at 270 &lt; 0 &gt; C for 15-30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe core was precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 3: 1 mixture of methanol and isopropanol. The isolated core was dissolved in hexane and used to form the core-shell material.

Synthesis of CdSe / CdZnS core-shell nanocrystals : 25.86 millimoles of trioctylphosphine oxide and 2.4 millimoles of octadecylphosphonic acid were loaded into a four-necked flask. The mixture was then dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdSe core was added to the reaction mixture. The hexane was removed under reduced pressure, and 2.4 mmol of 6-amino-1-hexanol was added to the reaction mixture. Dimethylcadmium, diethylzinc, and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. Cd and Zn were mixed in equimolar proportions while S was 2-fold excess for Cd and Zn. Cd / Zn and S samples were respectively dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 155 DEG C under nitrogen. The precursor solution was added dropwise at 155 &lt; 0 &gt; C over 2 hours using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in hexane.

Fabrication of layers containing semiconductor nanocrystals

Using a sample containing substantially prepared semiconductor nanocrystals according to one of the above-described examples dispersed in hexane, the films described in Table 1 were prepared (samples were prepared by mixing approximately 40 mg Of solids). Hexane was removed from the semiconductor nanocrystals at room temperature under vacuum. Care was taken to avoid over drying all solvents or removing them completely. 0.5 ml of RD-12, a low viscosity reactive diluent commonly available from Radcure Corporation (NJ 07004-3401 Fairfield, 9 Ode Ray Pl) was added to the semiconductor nanocrystals with magnetic stirring. After pre-dissolution of the semiconductor nanocrystals in a reactive diluent, 2 ml of DR-150 (a UV-curable acrylic formulation typically available from Radcure) was added dropwise with vigorous stirring. Occasionally, the mixing vial was heated to lower the viscosity and aid in agitation. After the addition was complete, the vacuum was removed to remove entrained air. The vial was then placed in an ultrasonic bath (VWR) for 1 hour to overnight to obtain a clear colored solution. Care was taken so that the temperature did not exceed 40 ° C while the sample was in the ultrasonic bath.

Several batches of semiconductor nanocrystals of the same color were mixed together in a UV curable acrylic. For the following samples, the three red ash listed in Table 1 were added together and the four green ash listed in Table 1 were added together.

The sample was coated on a pre-cleaned glass slide by a Meyer rod and cured for 10 seconds in a 5000-EC UV light cured flood lamp (DYMAX Corporation system) with an H-bulb (225 mW / cm ² ).

Samples containing multiple layers were cured between layers to achieve the desired thickness. A sample comprising a filter above (or below) the semiconductor nanocrystal / matrix layer has a filter coated by a Meyer rod in a separate step. A UV-curable pigment ink formulation (coat / line chemistry) is formulated to form the filter. The filter composition was formulated by adding together the weighted absorbances of the respective colors to achieve the desired transmittance characteristics.

Examples of other modifications for synthesizing semiconductor nanocrystals with aromatic surface functionalities include: An overcoating process can be performed in the absence of a ligand having an aliphatic group. In other words, the procedure can be carried out without the use of trioctylphosphine oxide (TOPO) or trioctylphosphine (TOP) and instead a non-coordinating solvent (e.g. squalane) is used. In order to maintain the solubility of the semiconductor nanocrystals formed in this way, the crystallization or ordered filling of the ligand species (both semiconductor-in-nanocrystals and semiconductor-inter-nanocrystals) is decomposed and the semiconductor nanocrystals are dispersed in various solvent systems A number of distinctly different aromatic phosphonic acid species and / or a number of distinct aromatic amine species may be included in the reaction. Alternatively, branched chain phosphonic acids and / or branched chain amines can be used for this purpose.

Example  5

Di-tert- tert -Butyl-4- Hydroxybenzylphosphonic acid  Manufacture of semiconductor nanocrystals capable of emitting red light

Synthesis of CdSe core : 1 mM cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine in a 20 mL vial at 100 &lt; 0 &gt; C, then dried and degassed for 1 hour. 15.5 millimoles of trioctylphosphine oxide and 2 millimoles of octadecylphosphonic acid were added to a three-necked flask, dried and degassed at 140 DEG C for 1 hour. After degassing, the Cd solution was added to the oxide / acid flask and the mixture was heated to 270 &lt; 0 &gt; C under nitrogen. Once the temperature reached 270 DEG C, 8 millimoles of tri-n-butylphosphine was injected into the flask. The temperature was returned to 270 캜 and 1.1 mL of 1.5 M TBP-Se was rapidly injected. The reaction mixture was heated at 270 &lt; 0 &gt; C for 15-30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe core was precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 3: 1 mixture of methanol and isopropanol. The isolated core was dissolved in hexane and used to form the core-shell material.

Di-tert- tert -Butyl-4- Hydroxybenzylphosphonic acid  Produce

3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid was obtained from PCI Synthesis (Massachusetts, USA, 01950 Newberryport Upper Tunnel Way 9).

Preparation of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid used the following synthetic approach:

3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid may be characterized by:

Melting point: 199-200 캜 [Lit: 200 캜; Reference: J. D.Spivack, FR1555941 (1969)]

IR: 3614 cm &lt; ^{-1 &} gt ;; 3593 cm ^-1 (approx., OH extension)

_{^{1 H-NMR (CD 3 OD}} ); δ 7.10 (d, _{aromatic, 2H, J P -H = 2.6Hz} ), 5.01 (s, exchanged with _{HOD), 2.99 (d, -CH 2} , 2H, J P -H = 21.2 Hz), 1.41 (s, -CH ₃ , 18H)

_{^{13 C-NMR (CD 3 OD}} ); C (CH ₃ ) ₂ (aromatic), 137.9 (aromatic), 126.2 (aromatic), 123.5 (aromatic), 34.41 (d, -C H ₂ , 35.75, 33.07, J _{P -C} = 537.2 Hz), 34.35 ) ₃ ), 29.7 (-C ( C H ₃ ) ₃ )

_{^{31 P-NMR (CD 3 OD}} ): δ 26.8

The above synthetic precursors included in the preparation of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid may be characterized by:

Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate:

Melting point: 119-120 DEG C [Lit: 118-119 DEG C; Reference literature: R. K. Ismagilov, Zhur. Obshchei Khimii, 1991, 61, 387]

IR: 3451 cm ^-1 (approx. OH extension); 2953 cm ^-1 (about, -CH ₃ , CH extension)

_{^{1 H-NMR (CDCl 3)}} ; δ 7.066 (d, Ar-H , 2H, J P -H = 2.8Hz), 5.145 (s, 1H, -OH), 4.06-3.92 (m, - C H 2 CH 3, 4H, HH and long range PH coupling), 3.057 (d, Ar- C H 2, 2H, J PH = 21.0 Hz), 1.412 (s, -C (C H 3) 3, 18H), 1.222 (t, -CH 2 C H 3, 6H)

_{^{13 C-NMR (CDCl 3)}} ; δ 153.98 (aromatic), 136.22 (aromatic), 126.61 (aromatic), 122.07 _{(aromatic), 62.14 (-O C H 2} CH 3, J P -C = 24.4Hz), 33.63 (Ar- C H 2, J P _{-C = 552.4Hz), 34.53 [-} C (CH 3) 3], 30.54 [-C (C H 3) 3], 16.66 (-CH 2 C H 3, J P -C = 24.4 Hz)

_{^{31 P-NMR (CDCl 3)}} : δ 28.43

Di-tert- tert -Butyl-4- Hydroxybenzyl  Bromide

Melting point: 51-54 DEG C [Lit: 52-54 DEG C; Reference: J. D. McClure, J. Org. Chem., 1962, 27, 2365]

IR: 3616 cm ^-1 (medium, OH extension), 2954 cm ^-1 (approx., Alkyl CH extension)

_{^{1 H-NMR (CDCl 3)}} ; δ 7.20 (s, Ar-H , 2H), 5.31 (s, -OH), 4.51 (s, -CH 2, 2H), 1.44 {s, [-C (C H 3) 3], 18H}

_{^{13 C-NMR (CDCl 3)}} ; -C (CH ₃ ) ₃ ], 34.6 (-CH ₂ ), 30.5 [-C ( C ₃ H ₃ )], ₃ ]

To prepare 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, other synthetic approaches known or readily apparent to those skilled in the art may be used.

CdSe / CdZnS  Synthesis of core-shell nanocrystals:

25.86 mmol of trioctylphosphine oxide and 2.4 mmol of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid were loaded into a four-necked flask. The mixture was dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was then cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdSe core was added to the reaction mixture. Hexane was removed under reduced pressure. Dimethylcadmium, diethylzinc and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. Cd and Zn were mixed in equimolar proportions, whereas S was 2-fold excess for Cd and Zn. The Cd / Zn and S samples were each dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 155 캜 under nitrogen. The precursor solution was added dropwise at 155 占 폚 over 2 hours using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in chloroform and used to form a semiconductor nanocrystal composite.

In Table 2, the 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ligand group is referred to as BHT.

Fabrication of layers containing semiconductor nanocrystals

The films described in Table 2 were prepared using samples containing semiconductor nanocrystals substantially prepared according to the synthesis described in Example 5. Bulk chloroform was removed from the nanocrystal sample by nitrogen purge. Residual chloroform was removed from the semiconductor nanocrystals under vacuum at room temperature. Care was taken to avoid over drying all solvents or removing them completely.

37 ml of RD-12, a low viscosity reactive diluent commonly available from Radcure Corporation (NJ 07004-3401 Fairfield, 9 Ode Ray Pl), was added to 4.68 grams of semiconductor nanocrystals under vacuum. The vessel was refilled with nitrogen and the mixture was mixed using a vortex mixer. After pre-dissolving the semiconductor nanocrystals in a reactive diluent, 156 ml of DR-150 (UV-curable acrylic formulation, commonly available from Radcure) was slowly added under vacuum. The vessel was refilled with nitrogen and the mixture was mixed using a vortex mixer.

Was then added to TiO ₂ (if displayed) of 2.00 g were mixed and the mixture using a homogenizer.

12.00 grams of hardener Escacure TPO was added and the mixture was then mixed using a homogenizer. The container containing the mixture was wrapped with a black tape to block the fluid from the light.

The vessel was then refilled with nitrogen and sonicated for at least about 3 hours. The sample was placed in an ultrasonic bath and care was taken so that the temperature did not exceed 40 ° C.

The sample was coated on a pre-cleaned glass slide by a Meyer rod and cured for 10 seconds in a 5000-EC UV light curing flood lamp (DYMAX Corporation system) with an H-bulb (225 mW / cm ² ).

The sample was taken out for evaluation, coated on a glass slide with 52 bars and cured for 10 seconds:

Thickness = 72 탆

Lambda em = 633.1 nm FWHM = 36 nm

% EQE = 50.5% A _450nm = 82.6%

Sometimes, the mixing vial was heated to lower the viscosity and aid in agitation. After the addition was complete, the vacuum was removed to remove entrained air. The vial was then placed in an ultrasonic bath (VWR) for 1 hour to overnight to obtain a clear colored solution. The sample was placed in an ultrasonic bath and care was taken so that the temperature did not exceed 40 ° C.

Multiple batches of semiconductor nanocrystals of the same color were mixed together. Prior to making the acrylic fabrication, the sample was coated by a Meyer rod on a pre-cleaned glass slide and exposed to a 5000-EC UV light curing flood lamp (DYMAX Corporation system) with an H-bulb (225 mW / cm ² ) And cured.

Samples containing multiple layers were cured between layers to achieve the desired thickness. The sample comprising the filter above (or below) the layer comprising the main material and the quantum limiting semiconductor nanoparticles has a filter coated by a Meyer rod in a separate step.

A filter was formed by blending a UV-curable pigment ink formulation from coat / line chemistry. (Examples include, but are not limited to, DXT-1935 and WIN 99). The filter composition was formulated by adding together the weighted absorbances of the respective colors to achieve the desired transmittance characteristics.

Film Features:

The films are characterized in the following manner:

· Thickness: Measured by micrometer

· Emission measurements measured in each type of sample 1 in Cary Eclipse. Excitation at 450 nm, 2.5 nm excitation slit, 5 nm emission slit

Absorbance measured at 450 nm in sample 1 of each type on Carry 5000. Baseline corrected with blank glass slide.

CIE coordinates measured in sample 1 of each type using a CS-200 Chroma Meter. The samples were excited at a 450 nm LED and the camera collected color data offsets.

· Measure external quantum efficiency (PL) using the method developed by Mello et al. (1). This method uses a collimated 450 nm LED source, integrating sphere and spectrometer. Take three measurements. First, the LED directly illuminates the integrating sphere to provide the spectrally labeled L1 in FIG. Then, a PL sample is placed in the integrating sphere so that only the diffused LED light irradiates the sample to provide the (L2 + P2) spectrum shown in Fig. Finally, the PL sample is placed in the integrating sphere so that the LED directly irradiates the sample (abnormal injection incident) to provide the (L3 + P3) spectrum shown in Fig. After collecting the data, calculate the respective spectral contributions (L's and P's). L1, L2 and L3 correspond to the sum of the LED spectra for each measurement, and P2 and P3 are sums associated with the PL spectrum for the second and third measurements. The following equation provides the external PL quantum efficiency:

EQE = [(P3 占)) - (P2 占 3)] / L1 占 (L2-L3)

For additional information regarding EQE measurements, see Mello et al., Advanced Materials 9 (3): 230 (1997), incorporated herein by reference.

In certain embodiments, semiconductor nanocrystals are purified prior to deposition.

In certain embodiments, the desired ligand can be attached to the semiconductor nanocrystals by forming the desired functionality in a phosphonic acid derivative, an amine derivative, or both. The following are non-limiting examples of general synthetic synthetic procedures for producing the desired phosphonic acid derivatives.

a) NaH, THF, NaI and 1

b) 1. TMSBr, CH ₂ Cl ₂ , 2.H ₂ O

Also, for more general synthetic procedures for the production of phosphonic acid derivatives, see: The Chemistry of Organophosphorus Compounds, Volume 4: Ter- and Quinque-Valent Phosphorus Acids and Their Derivatives, Frank R. Hartley (Editor), April 1996 .

In certain additional embodiments, the desired ligand can be attached to the semiconductor nanocrystals by forming the desired functionality in a phosphonic acid derivative, an amine derivative, or both. The following is a schematic, non-limiting example of a general synthetic procedure for producing the desired amine derivatives:

Example  6 - Natural Ligand  Semiconductor nanocrystals and cap exchanges fabricated to have Ligand  Of semiconductor nanocrystals

Example 6A - Preparation of semiconductor nanocrystals capable of emitting red light including natural ligands

Synthesis of CdSe core : 1 mM cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine in a 20 mL vial at 100 &lt; 0 &gt; C, then dried and degassed for 1 hour. 15.5 millimoles of trioctylphosphine oxide and 2 millimoles of octadecylphosphonic acid were added to a three-necked flask, dried and degassed at 140 DEG C for 1 hour. After degassing, the Cd solution was added to the oxide / acid flask and the mixture was heated to 270 &lt; 0 &gt; C under nitrogen. Once the temperature reached 270 DEG C, 8 millimoles of tri-n-butylphosphine was injected into the flask. The temperature was returned to 270 캜 and 1.1 mL of 1.5 M TBP-Se was rapidly injected. The reaction mixture was heated at 270 &lt; 0 &gt; C for 15-30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe core was precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 3: 1 mixture of methanol and isopropanol. The isolated core was dissolved in hexane and used to form the core-shell material.

Synthesis of CdSe / CdZnS core-shell nanocrystals : 25.86 millimoles of trioctylphosphine oxide and 2.4 millimoles of octadecylphosphonic acid were loaded into a four-necked flask. The mixture was dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was then cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdSe core was added to the reaction mixture. The hexane was removed under reduced pressure, and 2.4 mmol of 6-amino-1-hexanol was added to the reaction mixture. Dimethylcadmium, diethylzinc, and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. While Cd and Zn were mixed in equimolar proportions, S was 2-fold excess for Cd and Zn. The Cd / Zn and S samples were each dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 155 캜 under nitrogen. The precursor solution was added dropwise at 155 &lt; 0 &gt; C over 2 hours using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in hexane and their solution-state quantum yields were evaluated (QY about 80%).

Example 6B - Preparation of cap-exchanged semiconductor nanocrystals capable of emitting red light

Synthesis of CdSe core : 1 mM cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine in a 20 mL vial at 100 &lt; 0 &gt; C, then dried and degassed for 1 hour. 15.5 millimoles of trioctylphosphine oxide and 2 millimoles of octadecylphosphonic acid were added to a three-necked flask, dried and degassed at 140 DEG C for 1 hour. After degassing, the Cd solution was added to the oxide / acid flask and the mixture was heated to 270 &lt; 0 &gt; C under nitrogen. Once the temperature reached 270 DEG C, 8 millimoles of tri-n-butylphosphine was injected into the flask. The temperature was returned to 270 캜 and 1.1 mL of 1.5 M TBP-Se was rapidly injected. The reaction mixture was heated at 270 &lt; 0 &gt; C for 15-30 minutes while periodically removing an aliquot of the solution to track the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe core was precipitated from the growth solution in a nitrogen atmosphere glove box by adding a 3: 1 mixture of methanol and isopropanol. The isolated core was dissolved in hexane and used to form the core-shell material.

Synthesis of CdSe / CdZnS core-shell nanocrystals : 25.86 millimoles of trioctylphosphine oxide and 2.4 millimoles of octadecylphosphonic acid were loaded into a four-necked flask. The mixture was dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was then cooled to 75 DEG C and a solution of hexane (0.1 mmol Cd content) containing the isolated CdSe core was added to the reaction mixture. The hexane was removed under reduced pressure and then 2.4 mmol of decylamine was added to the reaction mixture. Dimethylcadmium, diethylzinc, and hexamethyldisilathane were used as Cd, Zn and S precursors, respectively. Cd and Zn were mixed in equimolar proportions, whereas S was 2-fold excess for Cd and Zn. The Cd / Zn and S samples were each dissolved in 4 mL of trioctylphosphine in a nitrogen atmosphere glove box. Once the precursor solution was prepared, the reaction flask was heated to 155 캜 under nitrogen. The precursor solution was added dropwise at 155 &lt; 0 &gt; C over 2 hours using a syringe pump. After shell growth, the nanocrystals were transferred to a nitrogen atmosphere globe box and precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in hexane and used for cap exchange reaction (QY about 80%).

Cap-exchange reaction for CdSe / CdZnS core-shell nanocrystals (1) : 10 ml of toluene and 42.6 mmol of 6-amino-1-hexanol were loaded into a four-necked flask. The flask was evacuated and refilled with nitrogen three times. The flask was then heated to 40 DEG C and a hexane solution containing the isolated CdSe / CdZnS core / shell (1 prep) was added to the reaction mixture. The mixture was heated at 40 &lt; 0 &gt; C overnight. Finally, cap-exchanged semiconductor nanocrystals were precipitated from the growth solution by adding hexane. The isolated core-shell nanocrystals were dissolved in a mixture of 3: 1 methanol and isopropanol and their solution-state quantum yield was evaluated (QY about 15%).

Cap-exchange reaction (2) for CdSe / CdZnS core-shell nanocrystals : 25.86 mmol of trioctylphosphine oxide, 2.4 mmol of octadecylphosphonic acid and 2.4 mmol of 6-amino- The flask was loaded. The mixture was dried and degassed in the reaction vessel by heating to 120 &lt; 0 &gt; C for about 1 hour. The flask was cooled to 40 占 폚 and a hexane solution containing the isolated CdSe / CdZnS core / shell (1 prep) was added to the reaction mixture. The mixture was heated at 40 &lt; 0 &gt; C overnight. Finally, the cap-exchanged semiconductor nanocrystals were precipitated from the growth solution by adding a 3: 1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were dissolved in hexane and their solution-state quantum yields were evaluated (QY about 19%).

Nanoparticles can have a variety of shapes including, but are not limited to, spheres, rods, discs, other shapes, and mixtures of various shape particles.

For example, metallic nanoparticles can be prepared as described in U.S. Patent No. 6,054,495, the entire contents of which are incorporated by reference. The metallic nanoparticles may be noble metal nanoparticles, such as gold nanoparticles. Gold nanoparticles can be prepared as described in U.S. Patent 6,506,564, the entire contents of which are incorporated by reference. Ceramic nanoparticles may be prepared, for example, as described in U.S. Patent 6,139,585, the entire contents of which are incorporated by reference.

Using previously established document procedures, narrow size distribution, high quality semiconductor nanocrystals with high fluorescence efficiency can be fabricated and used as building blocks. C. B. Murray et al., J. Amer. Chem. Soc. 1993, 115, 8706, B.O.Dabbousi et al., J. Phys. Chem. B 1997, 101, 9463), each of which is incorporated herein by reference in its entirety. Other methods known or easily identifiable by those skilled in the art may also be used.

In certain embodiments, the nanoparticles comprise chemically synthesized colloidal nanoparticles (nanoparticles), such as semiconductor nanocrystals or quantum dots. In certain preferred embodiments, the nanoparticles (e.g., semiconductor nanocrystals) have a diameter in the range of about 1 to about 10 nm. In certain embodiments, at least some of the nanoparticles, preferably all of the nanoparticles, comprise at least one ligand attached to the surface of the nanoparticles. See C. B. Murray et al., Annu. Rev.Mat.Sci., 30, 545-610 (2000), the entire contents of which are incorporated by reference. These zero-dimensional structures exhibit strong quantum confinement effects and can be used to design a bottom-to-top chemical approach to produce complex heterostructures with electronic and optical properties that can match the size of the nanocrystals.

When one or more nanocrystals are excited, emission from semiconductor nanocrystals at the emission wavelength can occur. The emission has a frequency corresponding to the band gap of the quantum confined semiconductor material. The band gap is a function of the size of the nanocrystals. Nanocrystals with small diameters may have intermediate properties between the molecular and bulk forms of the material. For example, nanocrystals based on semiconductor materials with small diameters can exhibit quantum confinement of both electrons and holes in all three dimensions, which leads to an increase in the effective band gap of the material as the crystallite size decreases . As a result, as the crystallite size decreases, both the optical absorption and emission of the nanocrystals are displaced to blue (i.e., higher energy).

Emission from the nanocrystals can be a narrow gaussian emission band that can be tuned over the entire wavelength range of ultraviolet, visible or infrared region spectra by varying the size of the nanocrystals, the composition of the nanocrystals, or both. The narrow size distribution of a population of nanocrystals can emit light in a narrow spectral range. The population may be monodisperse and may exhibit an rms deviation of less than 15%, preferably less than 10%, and more preferably less than 5% at the nanocrystal diameter. Spectral emission can be observed in a narrow range of total width (FWHM) at about 75 nm or less, preferably 60 nm, more preferably at most 40 nm, most preferably at most 1/2 or less. As the density of the nanocrystal diameter is reduced, the width of the emission is reduced.

Semiconductor nanocrystals can have high emission quantum efficiencies of 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%. III-VI group compound, IV-VI group compound, I-III-VI group compound, II-VI group compound, II-VI group compound, ZnS, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TlN, TlP, TlAs, TlSb, PbS, PbSe, PbTe or mixtures thereof.

Examples of methods for producing monodisperse semiconductor nanocrystals include pyrolysis of an organometallic reagent, such as dimethylcadmium, and implantation into a high temperature coordination solvent. This enables separate nucleation and as a result, the growth of visible nanocrystals is controlled. The preparation and manipulation of nanocrystals are described, for example, in U.S. Patent 6,322,901, the entire content of which is hereby incorporated by reference. This manufacturing method of nanocrystals includes a colloidal growth method. Colloid growth occurs by rapidly injecting M donors and X donors into a high temperature coordination solvent. The implant produces nuclei and this can grow in a controlled manner to form nanocrystals. The reaction mixture can be slowly heated to grow and quench the nanocrystals. Both the average size and the size distribution of the nanocrystals in the sample depend on the growth temperature. The growth temperature required to maintain steady state growth increases with increasing average crystal size. Nanocrystals are a component of a population of nanocrystals. As a result of separate nucleation and controlled growth, the resulting population of nanocrystals has a narrow monodisperse distribution of diameters. The monodisperse distribution of diameters may also be referred to as size. After nucleation, uniform surface derivatization and regular core structure can be obtained by controlling the growth and quenching of the nanocrystals in the coordination solvent. As the size distribution is sharp, the temperature can be raised to maintain steady state growth. By adding more M donors or X donors, the growth period can be shortened.

The M donor may be an inorganic compound, an organometallic compound, or an elemental metal. For example, M may be cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, or thallium. The X donor is a compound capable of reacting with the M donor to form a material having the formula MX. Typically, the X donor is a chalcogenide donor or a phonitide donor such as phosphine chalcogenide, bis (silyl) chalcogenide, dioxygen, ammonium salt or tris (silyl) phonitide. Suitable X donors include diacids, bis (trimethylsilyl) selenide ((TMS) ₂ Se), trialkylphosphine selenides such as (tri-n-octylphosphine) selenide (TOPSe) Butylphosphine selenide (TBPSe), trialkylphosphine telluride such as (tri-n-octylphosphine) telluride (TOPTe) or hexapropylphosphorus triamideideurilide (HPPTTe), bis (trimethylsilyl) (TMS) ₂ Te), bis (trimethylsilyl) sulfide ((TMS) ₂ S), trialkylphosphine sulfides such as (tri-n-octylphosphine) sulfide (TOPS), ammonium salts such as ammonium halide (e.g., NH ₄ Cl), tris (trimethylsilyl) phosphide ((TMS) ₃ P), tris (trimethylsilyl) arsenide ((TMS) ₃ as), or tris (trimethylsilyl) antimonide ((TMS) ₃ Sb). In certain embodiments, the M donor and the X donor can be residues within the same molecule.

Coordination solvents can help control the growth of nanocrystals. The coordination solvent is a compound with a donor single pair and has, for example, a single electron pair available for coordination to the surface of the growing nanocrystals. Solvent coordination can stabilize the growing nanocrystals. Typical coordinating solvents include alkylphosphines, alkylphosphine oxides, alkylphosphonic acids, or alkylphosphinic acids, but other coordinating solvents such as pyridine, furan and amines may be suitable for nanocrystal production. Examples of suitable coordination solvents include pyridine, tri-n-octylphosphine (TOP), tri-n-octylphosphine oxide (TOPO), and tris-hydroxypropylphosphine (tHPP). A technical grade TOPO may be used.

In certain methods, non-coordinating or weakly coordinating solvents may be used.

The size distribution during the growth phase of the reaction can be estimated by measuring the absorption line width of the particles. Changing the reaction temperature in response to changes in the absorption spectrum of the particles allows for a sharp particle size distribution to be maintained during growth. The reactants can be added to the nucleation solution during crystal growth to grow larger crystals. By stopping the growth at a specific nanocrystal average diameter and selecting an appropriate composition of the semiconductor material, the emission spectrum of the nanocrystals can be continuously matched in the wavelength range of 300 nm to 5 micrometers.

The semiconductor nanocrystals may include, for example, inorganic crystallites having a diameter of from about 1 nm to about 1000 nm, preferably from about 2 nm to about 50 μm, more preferably from about 1 nm to about 20 nm (eg, about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 nm).

Semiconductor nanocrystals typically have a diameter of less than 150 ANGSTROM. The population of nanocrystals preferably has an average diameter ranging from 15 A to 125 A.

Nanocrystals can be a component of a population of nanocrystals with a narrow size distribution. Nanocrystals can be spheres, rods, discs or other forms. The nanocrystals may comprise a core of semiconductor material. The nanocrystals may comprise a core having the formula MX wherein M is a metal selected from the group consisting of one or more metals such as but not limited to cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, And X comprises at least one element of group IV, V or VI (e.g., but not limited to oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony or mixtures thereof) . III-VI group compounds, IV-VI group compounds, I-III-VI group compounds, II-IV-VI group compounds, II- VI group compounds and II-IV-V group compounds. In certain embodiments, the nanocrystals may comprise IV group elements.

The core may have overcoating on the surface of the core. Overcoating can be a semiconductor material having a composition that is different from the composition of the core. The overcoat of the semiconductor material on the surface of the nanocrystals can be selected from the group consisting of Group II-VI compound, Group II-V compound, Group III-VI compound, Group III-V compound, Group IV-VI compound, Group I- ZnS, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs , GaSb, GaSe, InN, InP, InAs, InSb, TlN, TlP, TlAs, TlSb, PbS, PbSe, PbTe or mixtures thereof. In certain embodiments, the nanocrystals may comprise Group IV elements.

For example, ZnS, ZnSe or CdS overcoating can be grown on CdSe or CdTe nanocrystals. Overcoating methods are described, for example, in U.S. Patent No. 6,322,901. By controlling the temperature of the reaction mixture during overcoating and tracking the absorption spectrum of the core, an overcoated material with high emission quantum efficiency and narrow size distribution can be obtained.

The particle size distribution can be further refined by size selective precipitation using a poor solvent for nanocrystals, such as methanol / butanol as described in U.S. Patent No. 6,322,901. For example, nanocrystals can be dispersed in a solution of 10% butanol in hexane. Methanol may be added dropwise to this stirring solution until the milky white persists. Separation of the supernatant and agglomerates by centrifugation results in a precipitate containing the largest crystallite in the sample. This procedure can be repeated until no further sharp edges of the optical absorption spectrum are noted. Size-selective precipitation can be performed in a variety of solvent / solvent pairs, including pyridine / hexane and chloroform / methanol. The size-selected nanocrystal population may have an rms deviation of less than or equal to 15%, preferably less than or equal to 10%, and more preferably less than or equal to 5%, from the mean diameter.

Transmission electron microscopy (TEM) can provide information about the size, shape and distribution of the population of nanocrystals. The powder x-ray diffraction (XRD) pattern can provide the most complete information about the type and quality of the crystal structure of the nanocrystals. The size can be estimated because the particle diameter is inversely related to the peak width through the X-ray agglomeration length. For example, the diameter of the nanocrystals can be measured directly by transmission electron microscopy, or can be estimated from x-ray diffraction data using, for example, the shear error equation. It can also be estimated from the UV / Vis absorption spectrum.

Narrow FWHM of nanocrystals can lead to saturated color emission. Because the photons in the nanocrystal emission system are not lost to infrared and UV emissions, this can lead to efficient nanocrystal-color emission devices even in the red and blue portions of the spectrum. Saturated color emissions that can be broadly coordinated across the entire visible light spectrum of a single material system are not matched by any class of organic chromophore. In addition, the environmental stability of covalently bonded inorganic nanocrystals suggests that when the nanocrystals are used as the luminescent center, the lifetime of the hybrid organic / inorganic luminescent device should match or exceed the lifetime of all the organic luminescent devices. Retardation of the band edge energy level of the nanocrystals promotes capture and radiation recombination of all possible excitons, whether generated by direct charge injection or by energy transfer. Therefore, the maximum theoretical nanocrystal-light emitting device efficiency is comparable to the integration efficiency of the phosphorescent organic light emitting device. The excited state lifetime (τ) of nanocrystals is much shorter (τ ≈ 10 ns) than a typical phosphor (τ> 0.5 μs), which allows the nanocrystal-light emitting device to operate efficiently at high current densities.

Semiconductor nanocrystals according to the present invention may be used in a variety of applications including, but not limited to, for example, International Application No. PCT / US2007 / 013152 ("Light Emitting Devices and Displays with Improved Performance ", QD Vision, Inc., And other optoelectronic and electronic devices, including those described in commonly owned US patent application Ser.

Semiconductor nanocrystals in accordance with the present invention include, but are not limited to, U.S. Application No. 60/971885 (Coe-Sullivan et al., "System, Apparatus and Composition Including Optical Components, Optical Components", filed September 12, 2007) And those described in US application 60/973644 ("Optical components, systems, devices and compositions comprising optical components, Coe-Sullivan et al., Filed September 19, 2007) The entire contents of which are hereby incorporated by reference).

Other materials, techniques, methods, applications, and information that may be useful in the present invention are described in International Patent Application PCT / US2007 / 24750 entitled " Advanced Composites and Devices Containing Nanoparticles ", Coe-Sullivan et al. 2007 (Filed December 3, 2007) and U.S. Application No. 60/971887 (entitled "Functionalized Semiconductor Nanocrystals and Methods", Breen et al., Filed September 12, 2007) and International Application No. PCT / US2007 / 014711 QD Vision, Inc. et al., Filed on June 25, 2007, each of which is incorporated herein by reference in its entirety for all purposes, Quot;).

The singular forms used herein include the plural unless the context clearly dictates otherwise. Thus, for example, reference to emissive materials includes reference to one or more of these materials.

Whenever an amount, concentration, or other value or parameter is given as a range, a preferred range, or a desirable upper limit and a preferred lower limit, the upper limit or the lower limit or a pair of desirable values, whether or not the range is separately disclosed, Quot; is to be understood as particularly disclosing the entire range of the invention. When a numerical range is recited in the specification, unless otherwise stated, the range is interpreted as including its endpoint and all integers and fractions within the range. It is to be understood that the scope of the present invention is not limited to the specific numerical values recited when defining the scope.

The terms and expressions used herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding equivalents of the features described or described herein or portions thereof, It is understood that various modifications are possible within the scope. Further, without departing from the scope of the present invention, any one or more of the features of the embodiments of the present invention may be combined with one or more other features of other embodiments of the present invention. Additional embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and scope of the invention being indicated by the following claims and equivalents thereof.

All patents, patent applications and publications mentioned above are incorporated by reference in their entirety for all purposes. Neither the patent, the patent application nor any of the disclosures referred to herein are prior art.

Claims (93)

Wherein at least one of the ligands is represented by the following formula: &lt; EMI ID = 25.1 &gt;
X-Sp-Z
X represents a secondary amine group, urea, thiourea, amide group, phosphone or arsonic group, phosphine or arsinic acid group, arsenate group, or arsine oxide group; Z represents (i) not only capable of transferring a particular chemical property to the nanoparticle, but also provides a specific chemical reactivity to the surface of the nanoparticle, and is a functional, bifunctional or multifunctional reagent, or a reactive chemical group, (Ii) at least one group selected from the group consisting of a cyclic group, a halogenated group and a polar aprotic group, or (iii) both of the above (i) and (ii) Z is not reactive when exposed to light). The nanoparticle of claim 1, wherein Z does not make the nanoparticles dispersible in a liquid medium comprising water. delete The nanoparticle of claim 1, wherein the cyclic group comprises a saturated or unsaturated cyclic or bicyclic compound or an aromatic compound. delete The nanoparticle of claim 1, wherein the halogenating group comprises a fluorinating group, a perfluorinating group, a chlorinating group, a perchlorating group, a brominating group, a perbrominating group, an iodinating group, or a periodinated group. The nanoparticle of claim 1, wherein the polar aprotic group comprises a ketone, aldehyde, amide, urea, urethane or imine. The nanoparticle of claim 1, comprising a semiconductor material. The nanoparticle of claim 1, comprising a semiconductor nanocrystal. The nanoparticle of claim 1, comprising a core comprising a first material and a shell disposed over at least a portion of the core surface and comprising a second material. 11. The nanoparticle of claim 10, wherein the first material comprises a semiconductor material. 11. The nanoparticle of claim 10, wherein the second material comprises a semiconductor material. 11. The nanoparticle of claim 10, wherein the at least one additional shell is disposed on at least a portion of the surface of the shell. 10. The nanoparticle of claim 9, wherein the semiconductor nanocrystal comprises a core comprising a first material and a shell disposed over at least a portion of the core surface and comprising a second material. 10. The compound according to any one of claims 1 to 9, wherein the ligand represented by the formula X-Sp-Z is benzylphosphonic acid, a benzylphosphonic acid containing at least one substituent group on the ring of the benzyl group, Nanoparticles comprising a mixture comprising at least one of the foregoing. 10. The process according to claim 1 or 9 wherein the ligand represented by the formula X-Sp-Z is selected from the group consisting of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, Containing nanoparticles. The nanoparticle according to any one of claims 1 to 9, wherein the ligand represented by the formula X-Sp-Z comprises an organic amine or a fluorinated organic amine containing a terminal hydroxyl group. 15. A process according to any one of claims 1 and 8 to 14, comprising a natural ligand having at least two different chemical compositions attached to a surface, wherein at least one of said ligands has the formula X-Sp-Z The nanoparticles that are displayed. delete delete delete delete delete 15. The method of any one of claims 1 and 8 to 14, comprising a natural ligand having two or more different chemical compositions attached to a surface, wherein the first ligand has the formula
X-Sp-Z
(In the above formula, X represents a secondary amine group or an amide group)
The second ligand is a compound of formula
X-Sp-Z
(Wherein X represents a phosphone or an arsonic acid group, a phosphine or arsinic acid group, an arsanate group or an arsine oxide group)
Wherein each of Sp and Z on the first ligand and the second ligand may be the same or different. 2. The nanoparticle of claim 1 wherein the spacer group is a moiety capable of transferring charge. 2. The nanoparticle of claim 1, wherein the spacer group is an isomer. delete delete delete Reacting a precursor to form nanoparticles with a predetermined composition in the presence of a ligand having at least one different chemical composition, wherein at least one of the ligands is represented by the formula: .
X-Sp-Z
X represents a secondary amine group, an amide group, a phosphone or an arsonic acid group, a phosphine or arsinic acid group, an arsenate group, or an arsine oxide group; Sp represents a spacer group; (i) not only can transfer specific chemical properties to the nanoparticles, but also provide specific chemical reactivity to the surface of the nanoparticles, and can include functional groups such as functional, bifunctional or multifunctional reagents, or reactive chemical groups, , Or (ii) at least one group selected from the group consisting of a cyclic group, a halogenated group and a polar aprotic group, or (iii) both of the above (i) and (ii) Not reactive when exposed). delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete Comprising reacting a precursor for a predetermined composition in the presence of a ligand having at least one different chemical composition, wherein at least one of the ligands is represented by the formula: &lt; EMI ID = &Lt; / RTI &gt;
X-Sp-Z
X represents a secondary amine group, an amide group, a phosphone or an arsonic acid group, a phosphine or arsinic acid group, an arsenate group, or an arsine oxide group; Sp represents a spacer group; (i) not only can transfer specific chemical properties to the nanoparticles, but also provide specific chemical reactivity to the surface of the nanoparticles, and can include functional groups such as functional, bifunctional or multifunctional reagents, or reactive chemical groups, , Or (ii) at least one group selected from the group consisting of a cyclic group, a halogenated group and a polar aprotic group, or (iii) both of the above (i) and (ii) Not reactive when exposed). 60. The method of claim 30 or 59, wherein Z does not render the nanoparticles dispersible in the liquid medium comprising water. The method of claim 30 or 59, wherein the nanoparticles comprise a semiconductor material. 60. The method of claim 30 or 59, wherein the nanoparticles comprise semiconductor nanocrystals. 60. The method of claim 59, wherein the predetermined composition comprises a semiconductor material. 60. The method of claim 30 or 59, wherein the precursor comprises at least one metal-containing precursor and at least one chalcogen-containing or phonitogen-containing precursor. delete The method of claim 30 or 59, wherein the cyclic group comprises a saturated or unsaturated cyclic or bicyclic compound or an aromatic compound. delete The method of claim 30 or 59, wherein the halogenating group comprises a fluorinating group, a perfluorinating group, a chlorinating group, a perchlorating group, a brominating group, a perbrominating group, an iodinating group or a periodate group. The method of claim 30 or 59, wherein the polar aprotic group comprises a ketone, an aldehyde, an amide, a urea, a urethane or an imine. 60. The method of claim 59, wherein at least one coating material is formed over at least a portion of the nanoparticle surface. The method of claim 30 or 59, wherein the ligand represented by the formula X-Sp-Z is benzylphosphonic acid, a benzylphosphonic acid containing at least one substituent group on the ring of the benzyl group, And mixtures comprising at least one of the foregoing. The method of claim 30 or 59, wherein the ligand represented by the formula X-Sp-Z is selected from the group consisting of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate of an acid, &Lt; / RTI &gt; The method of claim 30 or 59, wherein the ligand represented by the formula X-Sp-Z comprises an organic amine or a fluorinated organic amine comprising a terminal hydroxyl group. 60. The method of claim 30 or 59 wherein the reaction is carried out in a liquid medium. The method of claim 30 or 59, wherein the spacer group is a moiety capable of transferring charge. 60. The method of claim 30 or 59 wherein the spacer group is an isomer. 65. The method of claim 64, wherein the molar ratio of the total moles of metal contained in the overcoated nanoparticles to the total moles of ligand represented by the formula X-Sp-Z ranges from 1: 0.1 to 1: 100. delete delete 74. The method of claim 74, wherein the molar ratio of the total moles of liquid medium to the total moles of ligand represented by the formula X-Sp-Z ranges from 500: 1 to 2: 1. delete delete The method of claim 30 or 59, wherein the precursor is reacted in the presence of a ligand having two or more different chemical compositions, wherein at least one of the ligands is represented by the formula X-Sp-Z. delete delete delete 59. The method of claim 30 or 59 wherein the precursor is reacted in the presence of a ligand having two or more different chemical compositions,
X-Sp-Z
(In the above formula, X represents a secondary amine group or an amide group)
The second ligand is a compound of formula
X-Sp-Z
(Wherein X represents a phosphone or an arsonic acid group, a phosphine or arsinic acid group, an arsanate group or an arsine oxide group)
Wherein each of Sp and Z on the first ligand and the second ligand may be the same or different. delete 87. The method of claim 87, wherein X in the second ligand represents a phosphone or arsonic acid group or a phosphine or arsinic acid group, the first ligand and the second ligand are initially present in equimolar amounts, The X-group content of the first ligand and the acid group content of the second ligand. delete delete delete delete

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